Certain quaternary ammonium compounds



May 14, 1957 M. DE GRooTE ETAI.

CERTAIN QUATERNARY AMMONIUM COMPOUNDS Filed April 4. 1955 PERCENTAGE OF OXIDE IGNORING PRESENCE OF ONE MOLE OF WATER PER MOLECULE INVENTORSZ MELVIN DE GROOTE v BERNHARD KEISER .MMM

ATTORNEY CERTAIN QUATERNARY ANIMONIUM COMPOUNDS Melvin De Groote, University City, and Bernhard Kaiser,

Webster Groves, Mot, assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware Application April 4, 1955, Serial No. 499,196

13 Claims. (Cl. 260-295) The present invention has a number of aspects. One aspect is concerned with the conversion of a certain specific type of polyalkyleneglycol, as hereinafter de scribed, into a carboxyl derivative in which the carboxyl group contains a labile chlorine atom followed by reaction with the tertiary amine.

A second aspect is concerned with the product so derived by the above procedure.

A third aspect is concerned with uses for such polyalkyleneglycol derivatives and particularly uses other than the resolution of petroleum emulsions.

Attention is directed to our `co-pending application, Serial No. 499,197, filed April 4, 1955, in which we have 2,722,400 Patented May T144, i957 which water, propyleneglycol, or low molal propyleneglycol is oxypropylated by means of any suitable catalyst, either acid or alkaline, and then subjected to oxyethylation. Instead of being a single step process, one may employ a two-step process in which oxypropylation takes place iirst and then oxyethylation. If desired, one can simply purchase a suitable polypropyleneglycol from any one of a number of sources and subject the product to oxyethylation as hereinafter specified. If desired, one can purchase the oxyethylated propyleneglycols in the open market and thus the first step is merely esterication, followed by the second step which involves conversion into a quaternary ammonium compound.

As has been stated previously, the polyalkyleneglycols employed are reactants obtained by the oxyethylation of polypropyleneglycol. In a general way, the composition of such polyalkyleneglycol is such that the molecular weight range varies from approximately 800 up to approximately 10,000. The amount of ethylene oxide present in the compound as compared with the oxypropyleneglycol varies from 10% to 20% up to approximately 80% to 90%. Indeed, this is the generally accepted procedure for the characterization of such product. Thus the table employed by one manufacturer is as follows in which the X marks indicate products regularly available and those available in carload or large quantities appear with specific designations other than an X mark.

TABLE I CHARACTERIZATIONl OF OXYETHYLATED POLYPROPYLENEGLYCOLS Ethylene oxide ln molecule, percent First Second digit digit Molecular weight of base unit:

Less than 600 (1) 601-80 (2) (3) X X X X (4) X L44 X (5) (6) L61 L62 L64 X X L74 X L77 0 8) X L84 L87 L88 More than 2,500 (9) s.

pointed out that a narrow sub-genus selected from the broad group herein described is particularly eective for the resolution of petroleum emulsions of the water-inoil type.

For purpose of convenience, what'is said hereinafter will be divided into ve parts:

Part 1 is concerned with the preparation of polyalkyleneglycols employed as initial reactants;

Part 2 is concerned with the description of suitable halogenated monocarboxy acids which can be employed in the present invention;

Part 3 is concerned with the preparation of esters by reaction between the two classes of reactants previously noted;

Part 4 is concerned with a description of the tertiary amines which can be employed to convert the esters described in Part 3, preceding, into quaternary or diquaternary compounds;

Part 5 is concerned with uses for the quaternary compounds obtained in the manner described in Part `4 and particularly for applications other than those involving the resolution of petroleum emulsions of the Water-inoil type.

PART l The preparation of the polyalkyleneglycols which are used as initial reactants, can be a continuous process in The manufacture of ethyleneglycol, polyethyleneglycol, propyleneglycol, polypropyleneglycol, and oxyethylated polypropyleneglycol, is well known. One procedure, of course, is to simply oxypropylate water so as to obtain the polypropyleneglycol of the desired molecular weight, for instance, in the range of 500 or thereabouts, to approximately 2500 or 2000, and then to oxyethylate so as to obtain an oxyethylated polypropyleneglycol coming within the indicated range.

However, one need not start with water and one may start with a low molal water-soluble glycol, for instance, propylene, dipropylene or tripropyleneglycol.

If desired one may purchase the polypropyleneglycol in the open market. For instance, one manufacturer regularly manufactures polypropyleneglycol within the following three molecular weight classes, to Wit, 400-450; 975-1075; and 1950 to 2100. Higher molecular weights are also available as, for example, at least one product having a molecular weight of approximately 2750 orv fb 31 It is not believed that any description of the manufacture of such products is required but purely for purpose of illustration reference is made to U. S. Patent No. 2,674,619, dated April 6, 1954, to Lundsted. In said patent there is a characterization of such products in the following language: i

18. Compounds having improved detergent properties,

according to the formula where y equals at least and (C2H4)5..m' equals -90% of the total weight of the compound.

In any oxyalkylation procedure of the 1sind herein-described, particularly since a multiple oxyallgylation is involved (i. e., oxyallgylation with at leastY 2 different oxides), it is well known that onedoes not obtain a single compound but a cogeueric mixture. VIndeed this is true of even the simplest oxyallylation as, kfor example, the oxyalkylation of a monohydric alcohol. Reference is made to U. S. Patent No. 2,679,513, dated May 25, 1954, to De Groote with particular reference to ,columns 19 and 20. Y

For reasons which have been stated previously, two or three diierent manufacturers may furnish a polypropyleneglycol 1200 or 1500, or 2000, or even 3000 or 4000, or the like, and although substantially the same there is a slight variation in composition. The reason is due toV at least two factors. As pointed out previously one does not get a single product but one obtains cogeneric mixtures whose average composition corresponds to the molecular Weight indicated. For instance, one manufacturer of a polypropyleneglycol whose average molecular weight is 1025 states the molecular weight in fact varies from 975 to 1075 and, similarlyin the case of-a product whose-iy average molecular weight is 2025 the variation runsfrom 1950 to 2100. Depending on the catalyst used, the rate of` reaction and other factors the variation may be even somewhat wider, for instance, 1025 to 1125 in one case and 1900 and 2150 in another case.

of propylene oxide.

ume 40, 1953, pages 221-9, 249-58, and'281-6.

Since propyleneglycol has both a primary alcohol and Y' a secondary alcohol radical and since one can look upon polypropyleneglycols as polymeric linear condensation derivatives of propyleneglycol it is obvious one could obtain head-to-head polymerization,` tail-to-tailpolymerization, and h ead-to-tail polymerization. This simply means the equivalent of etherization involving 2 primary hydroxyl groups or 2 secondary hydroxyl groups, or a pri,- mary and secondary hydroxyl group. This is illustrated by the fact that there are three dipropyleneglycols. If one goes to tripropyleneglycol there are theoretically at least eight possibilities. In the higher polypropyleneglycols these possibilities increase enormously. Thus, the rst variation is in the molecular` Weight size which determines the average molecular weight and the second variation is4 concerned with the fact that dependent on the method of oxypropylation employed, andl various factors such as catalyst used, temperature, pressure, speed of reaction, etc., there may be variations in the actualY structure. For this reason solubility in water must be interpreted in light of such fact and, thus, although polypropyleneglycol ofran average molecular weight of` 1,000 or thereabouts may show solubility of about 1.5% in water actually this may be the solubility of some of, the low molalcogeners. Thus, it is customary to consider polypropyleneglycols having a molecular weight of 1,000 or more as being substantially water-soluble. Suchcus- The otherv factor is one that has been pointed out a number ofV times Vand particularly in a series of articles dealing with 'derivatives See Les Derives de lOxyde de fi Propylene, parts I, IIV and III, Industrie Chimique, voltomary use is herein included. Even if the molecular weight i-s double, up to 2000 or thereabouts, there may even be a trace of the glycol which is water soluble, for instance, somewhere in the neighborhood of .015%.

In subsequent Table II the polypropyleneglycols obtained varied in molecular weight from approximately 1100 to 3600. They were obtained as the equivalent of reacting one mole of` water with 18 moles, 20 moles, 24 moles, 28 moles, 32 moles, 38 moles, 42 moles, 46 moles, and 59 moles of propyleneoxide. They were then reacted with small amounts of ethylene oxideyin some cases one to four moles, in other cases two to ve moles, or three to six moles, ve to seven moles, andjn other instances as many as 15 moles of ethylene oxide. Table 1I gives the data in complete form covering these oxyethylated polypropyleneglycols which were obtained by conventional procedures using an alkaline catalyst. The molecular weight, including the initial mole of water, is shown and also the percentage of the two oxides lignoring the initial moles of water so as to conform to the accompanying drawing.

TABLE 11 Ignoring initial Propyl- Ethyl- Molec. Molec. mole of water Molec. Ex.No. ene ene wt. Wt. wt.i11 oxide, oxide, contribcontribcluding moles moles uted uted Percent Percent l mole by PrO byEt PrO E water 13 1 1, 044 44 95. 96 4. 04 1, 106 13 2 1, 044 33 92. 23 7. 77 1, 150 13 3 1, 044 132 33.77 11.23 1,194 13 4 1, 044 176 35. 53 14. 42 1, 233 20 1 1, 160 44 96. 35 3. 65 1, 222 20 2 1, 160 33 92. 95 7. 05 1, 266 20 3 1, 160 132 39. 79 10. 21 1, 310 20 4 1, 160 176 36. 32 13. 13 1, 354 24 2 1, 392 s3 94. 05 5. 95 1, 493 24 3 1, 392 132 91. 34 3. 66 1, 542 24 4 1,392 176 33.77 11.23 1,536 24 5 1, 392 220 76. 35 13. 65 1, 630 2s 2 1, 624 33 94. 37 5. 13 1, 730 23 3 1, 624 132 92. 43 7. 52 1, 776 23 Y 4 1,624 176 90.22 9. 73 1,320 23- 5v 624 220 33. 09 11. 91 1, 364 32 3 1, 356 132 93. 36 6. 64 2, 006 32 4 1, 356 176 91. 33 3. 67 2, 050 32 5 1, 356 220 39. 40 10. 60 2, 096 32 6 1, 356 264 37.47 12. 43 2, 140 33 4 2,204 176 92.60 7.40 2,393 33 5 2, 204 220 90. 93 9. 07 2, 442 33 6 2, 204 264 39. 30 10. 70 2, 436 33 7 2, 204 303 37. 75 12. 25 530 42 5 2, 436 220 91. 72 3. 23 2, 674.. 42 6 2, 436 264 90. 22 3. 73 2, 713 42 7 2, 436 303 33. 734 11. 22 2, 762 42 s 2, 436 352 37. 39v 12. 61 2, 306 46 6 2, 663 264 91. 00 9. 00 2, 950 46 7 2, 663 303 39. 65 10. 35 2, 994 46 3. 2, 663 352 3s. 35 11. 65 3,033 46 9 663 336l 37. 09 12. 91 3, 032.- 50 3 2, 900 352 39; 13 10. 32 3, 270 50 9. 2, 900 396 37.99 12.01 3, 314 50 10` 2, 900l 440 36. 33 13. 17 3, 353 .50 11 2, 900V 434 35. 70 14. 30` 3, 402 50 12 2, 900 523 34. 60 15. 40 3, 446 5o 13 2, 900 572 33. 52 16. 43 3, 490 50 14 2, 900 616 32. 47A 17. 53 3, 534 50 15 2, 900 660 31.47 1s. 53. 3, 573

PART 2.

Having obtained an oxyethylated propyleneglycol of the kind described-in Table I as available in the open market o rprepared in the manner described-in. Table II, orrvariantsthereof, the next step is reaction with a suitablefollowing:

substituted acyl halides, and esterfying derivatives are suitable, particularly alpha-halogen carboxylic acids of not over 6 carbon atoms. When the halogen is in the alpha-position to the CO group, the reaction seems Vto go with greater readiness. And with the shorter chain esterifying halogen carboxylic acids or their functional equivalents, especially chloroacetyl chloride, the reaction goes with such ease that this may in fact be considered an invention within the broader aspect. Other halogen acylating compounds which are suitable are, for example, alpha-chlorpropionic acid, alpha-bromstearic acid, alphabromoleic acid, or the acyl halides or anhydrides corresponding to these acids.

PART 3 Esters are obtained by the usual esteritication procedures involving the diols as described in Part 1 with 20 the chlorocarboxy acids described in Part 2, preceding. The procedure is illustrated by the following examples.

Example 1b 25 Example 2b i 4.0

The same procedure was followed as in Example lb, except that instead of one mole of chloroacetic acid, 2 moles or 189 grams were added and the mixture was 45 heated as before to remove 2 moles of water or 36 grams `by distillation. A non-viscous amber colored water -emulsiable liquid resulted.

Further examples are illustrated in Tables III and IV, 50

TABLE III.

i afraaaoo TABLE IV Ex. Molar Temp., Time, Grams Moles Grams No. ratio O. hours water water xylene distilled distilled used PART 4 Having obtained an ester in which there is one or two halogenated carboxy radicals obtained by reacting a diol of the kind described in Part 1 with either one or two moles of a halogenated acid or its equivalent as described in Part 2, such esters are then reacted with appropriate tertiary amines to give a quarternary ammonium compound. Suitable tertiary amines include pyridine, trimethylamine, triethylamine, tributylamine, triamylamine, etc. These are the typical tertiary amines which are commonly employed in this type of reaction. The production of suitable quaternary compounds in some instances having one quaternary radical and in other instances two, are illustrated subsequently.

The homologues of pyridine, for instance, the low molal alkyl derivatives such as the low molal derivatives of the monoethyl derivatives or the dimethyl or diethyl derivatives, are more expensive than pyridine but ultimately may be available at a cost which makes their use feasible. Such derivatives, as long as there is no interference with the quaternization of the tertiary nitrogen, are suitable.

Example 1c One molecular equivalent of Example l4b of Table III or 4153 grams, was heated under reux at 160 C. for

one hour with 2 moles of pyridine or 160 grams. Upon cooling a homogeneous Water soluble material resulted.

Example 2c The same procedure was followed as in Example 1c Moles Weight No. used in grams Acid.

Moles used Weight in grams Chloroacetic Alpha chlorpropionie- Alpha chlorbutyric.-. Alpha chloroleic Chleroacetic NNNNHNNNMNNNNNNNN Diols identified by number in the L series are from Table I; in the small a series are from Table II.

Note that Table IV immediately following presents further data in regard to Examples 1b through l7b. This is in effect a continuation of Table III. 75

except that instead of 4153 grams of Example 14b of Table III, 4181 grams of Example 1Gb of Table III was used. A homogeneous water soluble material resulted,

Further examples are illustrated in Table V following.

in which n is a small-wholenumber noLover 4,.and .ORO

TABLE V Ex. No. Ester'used Molar Wt. in Tertiary Moles Wt. in Molar Temp.,

equiv. grams amine gramsv 1 ratio cvC.

. 1 1 4, 153.0 Pyridine-- 2 160 172 160 1b 1 1, 963. 0 2 v160 1-2 f 160 3b 1 Y4, 699. 2 2 160 f 1-2 l16() 8b 1 4, 563.0 2 d 160 1-2v -160 PART s As has been pointed out previously, one of the sub- "genera Aherein described is'particularlyl effective in the resolution ofpetroleum'emulsions of Vthe water-in-oil type 'as rdescribed in our copending application, Serial No. v499,197, lfiled April 4, 1955. The products herein de- V'scribed "are effective for a variety of uses where cationic surfactantsareemployed. It is wellknown that cationic surfactants have utility 'inthe following elds: Acid de- 'tergents; lagricultural sprays; anti-static; asphalt; cement;

floa'ta'tion; leather; metals; paints; printing inks; rubber; 30 "and" textiles.

Reference 'ismade to certain other uses. For instance,

*the material is valuable as a fuel oil additive in the man- -ner described in U. S. Patent No. 2,553,183, dated May '15, 1951,-"to Caron et al. It Vcan be used in'substantially 35 thesame Vproportions or low'er proportions Aand vthis is particularly't'rue when used in conjunction with a glyoxalidine, or amido glyoxalidine.

' An analogous use in which these products are'equally satisfactory, is that described 'in U. S. Patent No. 40 2,665,978, dated January 12, 1954, to Stayner et al. The amount employed is`in the same proportion or lesser amounts than referred to in said aforementioned Caron et al. fpatent.

The second-use yis-for the purpose of inhibiting fogs in hydrocarbon products as Vdescribed in U. S. Patents Nos. 2,550,981 Aand 2,550,982, both dated May 1, 1951, and both to Eberz. Here, again, it can be used in the same proportions as herein indicated or even smaller proportions.

These materials also .-haveparticular utility in increasing the yield of `an oil Well by various procedures which in essence involve the use of fracturing of the strata by means of liquid pressure. A mixture of these products with oil or 1oil in combination with a gel former alone, 55 or a gel former and linely divided mineral particles, yields a product which, when it reaches crevices in the strata which are yielding water, forms a gelatinous mass of curdy precipitate or solid yor semi-solid emulsion yof a high viscosity. In any event, it represents a rapid gelling agent for the strata crevices and permits pressure to be applied to fracture the strata without loss of uid through crevices, openings or the like.

The herein described products and the derivatives thereof are particularly valuable in flooding processes for recovery of oil from subterranean oil-bearing strata when employed in the manner described in U. S. Patent No. 2,233,381, dated February 25, 1941, to De Groote and Keiser. p

Having thus described our invention, what we claim as 7 0 new and desire to secure by Letters Patent, is:

l. A quaternary ammonium compound of the structure is the residue of the oxyethylated polypropylencglycol HO-(C2H4O :(CsHeO )'1/(C2H4O) :v vH

where (C3HsO) equals 'at least 10, Aand (C21-140km# equals 10f90% of the Atotal weight'of the Yeompound,ithe

molecular Weight being within the range of approximately 800 Vto approximately 10,000 and 'o Il R'c is the radical tof the 'halogenated monocarboxy .acid

'(HalwRtioH having not over 18 carbon atoms in which Ris composed of rcarbon and hydrogen :atoms,.inrwhich n is a -smalllwhole number .not over 2 land the .halogen atom. is

substitutedfin the alpha-carbon position, and NERr is .the radical `of the free'tertiary amine yNE-Ri in which Rris composed of carbon and hydrogen atomsandrepresents not over 3 organic radicals having a total of not over 15 carbon atoms which organic radicals collectively satisfy the trivalent nitrogen v4valency, and R" is a member of the class consisting of hydrogen and ture ' RIENRC O R O CR'NE'RI] 4halogen in which ORO is the residue of the oxyethylated polypropyleneglycol Where (Cal-IeO)y-equals at least 10, and (C2H4O)z+e' equals 10,90% of the total weight of the compound, 'the `molecular weight-being within the range of Vapproximately 800 to approximately 10,000, l'and o Il t R'C isv the 'radical 'ofthehalogenated monocarboxy acid o (Hal) RLJOH having not over -18 carbon atoms in which R -is oomo Il [wormen/NER! halogen posed of carbon'. and hydrogen. atoms,':and the halogen vatom, is substituted in the alpha 'carboni position, .and

NER1 is the radicalo'fgthe'.freetertiary..amine NER; in

which R1 is composed of carbon and hydrogen atoms and represents not over 3 organic radicals having a total of not over 15 carbon atoms which organic radicals co1- lectively satisfy the trivalent nitrogen valency.

4. A quaternary ammonium compound of the structure l? o RrEN R' C O RO RNERs] chlorine in which ORO is the residue of the oxyethylated polypropyleneglycol where (C3Ha0)y equals at least 10, and (CzHrO)e+e' equals 10-90% of the total weight of the compound, the molecular weight being within the range of approximately 800 to approximately 10,000, and

i Re is the radical of the halogenated monocarboxy acid in which ORO is the residue of the oxyethylated polypropyleneglycol where (Cal-150),; equals at least 10, land (C2H4O)m+e' equals l-90% of the total weight yoi the compound, the molecular weight being within the range of approximately 800 to -approximately 10,000 and l Rf is the radical of the halogenated monocarboxy acid having not over 2 carbon atoms in which R is composed of carbon and hydrogen atoms, and the halogen atom is substituted in the alpha carbon position, and NERi is the radical of the free tertiary amine NERr in which R1 is composed of carbon and hydrogen atoms and represents not over 3 organic radicals having a total of not over 15 carbon atoms which organic radicals collectively satisfy the trivalent nitrogen valency.

6. The quaternary compound of claim 5 in which NERr is a lower molecular weight alkyl derivative of pyridine having not over 9 carbon atoms.

7. The quaternary compound of claim 5 in which Nz-Rr is pyridine.

8. A quaternary lammonium compound of the structure O O [(pyridlne) CHr O R O (u) CH: (pyrldtne)] [Cl] i in which ORO is the residue of the oxyethylated polypropyleneglycol where (CSHGOM equals at least 10, and (C2H4)+e! equals 10-90% of the total weight of the compound,`the molecular weight being within the range of approximately 800 to approximately 10,000.

9. A quaternary ammonium compound of the structure o o [(pyrmme) cmp: o Ro ii cmtpyridino] [C1] i in which ORO is the residue of the oxyethylated polypro pyleneglycol where (C3HeO)y equals approximately 40%, and (\C2H4O)x+x' equals approximately 60% of the total weight of the compound, the molecular weight being within the range of approximately 800 to approximately 10,000.

10. A quaternary ammonium compound of the struclll'e i l [(pyridine) C H2O O RO C CH2 (pyrldinwl [C1] in which ORO is the residue Vof the oxyethylated polypropyleneglycol where |(C3HO)y equals approximately 45%, and. (C2H4O)z+a' equals approximately 55% of the total. weight of the compound, the molecular weight being within the range of approximately 800 to approximately 10,000.

11. A quaternary ammonium compound of the structure 0 o [(pyridiue) ouali o R0 il; onupyridmo] [all in which ORO is the residue of the oxyethylated polypropyleneglycol ture t t (pyridine) C Hic 0 R o omtpyridln] [Cil in which ORO is the 4residue of the oxyethylated polypropyleneglycol where (CaHeOh, equals approximately 55%, and

(C2H4O)+e' equals approximately 45% of the total weight of the compound, the molecular weight being within the range of approximately 800 to approximately 10,000.

13. A quaternary ammonium compound of the structure t E (pyridine) 0R20 o R0 clmpyridmo] [C11 l1 1 in which ,ORO is the residue `of the oxyethylated polypropyleneglycol Y References Cited in the le of this patent UNITED STATES PATENTS YDe Groote et al..V May. 2, 1950 vDe: Groote :et va1.A -Aug. 1,1950 De Groote et ai. Aug. 1, 1950 De Groote et a1 Apr. 17, 1951 De Groote et al Apr. 17, 1951 Girod et a1. July 6, 1954 

1. A QUATERNARY AMMONIUM COMPOUND OF THE STRUCTURE 